Hydrogenation catalyst with improved textural properties

ABSTRACT

A method is provided for making a catalyst support, and includes the steps of providing an aqueous suspension of refractory inorganic oxide and refractory inorganic carbide; forming the suspension into droplets; exposing the droplets to a gelling agent whereby the droplets are at least partially solidified so as to provide substantially sphere-shaped portions of refractory inorganic oxide and refractory inorganic carbide; and drying and calcining the sphere-shaped portions so as to provide substantially spherical particles of catalyst support containing refractory inorganic oxide and refractory inorganic carbide. Catalytically active metal phases and hydrogenation processes using the catalyst are also described.

BACKGROUND OF THE INVENTION

The invention relates to a hydrogenation catalyst, a method for makingthe catalyst, and a hydrogenation process utilizing the catalyst,wherein the catalyst has desirable physical characteristics.

Hydrogenation processes are used for processing various hydrocarbonfeedstocks to obtain desirable products. Such processes utilize acatalyst to direct the reaction toward the desired products. Thecatalyst must be capable of withstanding the operating conditions of theprocess without rapidly losing effectiveness.

Numerous types of reactors can be used for carrying out thehydrogenation reaction. One type is known as an ebulliating bed reactor.An ebulliating bed reactor is characterized by a vessel containing a bedof the catalyst through which the feedstock is passed, typically fromthe bottom toward the top of the reactor. This results in a bed of thecatalyst suspended in the medium and subjected to continuous collisions.The catalyst itself remains inside the reactor.

One problem encountered in the art with ebulliating reactors is theattrition rate of the catalyst contained in the reactor. That is, thecatalyst tends to break down to smaller particles or fines after anysignificant amount of use.

U.S. Pat. No. 5,710,093 to Rivas et al. is drawn to a hydrogenationcatalyst, and utilizes a process which produces spherical catalystbodies that have good process properties and are resistant to attrition.Even greater improvements in the activity, heat dissipation andattrition resistance of the catalyst are of course desirable.

It is therefore a primary object of the present invention to provide acatalyst system wherein the catalyst particles are resistant toattrition.

It is a further object of the present invention to provide a catalysthaving good heat dissipation properties so as to assist in dissipatingheat generated by the exothermic hydrogenation reaction.

It is a still further object of the present invention to provide acatalyst system which has excellent activity and selectivity towarddesirable hydrogenation reactions for converting a carbon monoxidefeedstock to C₂+hydrocarbons.

Other objects and advantages of the present invention will appearhereinbelow.

SUMMARY OF THE INVENTION

According to the present invention, the foregoing objects and advantageshave been readily attained.

According to the invention, a method is provided for making a catalystsupport, wherein the method comprises the steps of providing an aqueoussuspension of refractory inorganic oxide and refractory inorganiccarbide; forming the suspension into droplets; exposing the droplets toa gelling agent whereby the droplets are at least partially solidifiedso as to provide substantially sphere-shaped portions of refractoryinorganic oxide and refractory inorganic carbide; and drying andcalcining the sphere-shaped portions so as to provide substantiallyspherical particles of catalyst support containing refractory inorganicoxide and refractory inorganic carbide.

Still further according to the invention, catalyst support is providedwhich comprises substantially spherical particles of a substantiallyhomogenous mixture of refractory inorganic oxide and refractoryinorganic carbide, the support having a solid surface area of at leastabout 65 m²/g, a particle size of at least about 0.1 mm and preferablybetween about 0.1 and about 3 mm, a pore volume of at least about 0.2cc/g, and an average pore diameter of at least about 150 Å.

In further accordance with the invention, a process is provided forhydrogenation of a carbon monoxide feed which method comprises the stepsof providing a catalyst system comprising a catalyst support and acatalytically active metal phase on the catalyst support, wherein thecatalyst support comprises substantially spherical particles of asubstantially homogenous mixture of refractory inorganic oxide andrefractory inorganic carbide, the support having a solid surface area ofat least about 65 m²/g, a particle size of at least about 0.1 mm andpreferably between about 0.1 and about 3 mm, a pore volume of at leastbout 0.2 cc/g, and an average pore diameter of at least about 150 Å, andthe catalytically active metal phase comprising at least one first metalselected from Group 4 of the periodic table of elements, and at leastone second metal selected from the group consisting of Groups 8, 9 and10 of the periodic table of elements; providing a carbon monoxide feed;and exposing the feed to the catalyst at hydrogenation conditions so asto convert the feed into a product comprising CH₄, CO₂ and C₂ ⁺. Theprocess of the present invention advantageously produces a conversionrate of at least about 60% vol. of the feed.

DETAILED DESCRIPTION

The invention relates to a hydrogenation catalyst, a method for makingthe catalyst, and a hydrogenation process utilizing the catalyst whereinthe catalyst has excellent activity toward desired hydrogenationproducts and good properties in connection with the dissipation of heat.The hydrogenation catalyst of the present invention includes a catalystsupport having desirable properties, and a catalytically active metalphase on the support which further provides the desired hydrogenationactivity. According to the invention, the catalyst support is producedin the form of substantially spherical particles of a substantiallyhomogenous mixture of refractory inorganic oxide, preferably silica, andrefractory inorganic carbide, preferably silicon carbide.

The support advantageously has a solid surface area of at least about 65m²/g, a particle size of at least about 0.1 mm and preferably betweenabout 0.1 and about 3 mm, a pore volume of at least bout 0.2 cc/g, andan average pore diameter of at least about 150 Å.

According to the invention, a method is also provided for making thecatalyst and catalyst support of the present invention.

The present method starts with provision of a suspension or slurry ofsilica, preferably colloidal or amorphous silica in water. Such asuspension or slurry can be readily prepared in many ways well known toa person of ordinary skill in the art. One preferred method forpreparing the suspension is to mix a water soluble refractory inorganicsalt, for example sodium silicate, with water to provide the desiredsuspension.

It is preferable to keep the viscosity of the suspension at a level highenough to keep the silica in suspension, preferably at a viscosity of atleast about 10 cp at 25° C. To this end, it may be desirable to add aviscosity agent to the suspension. One example of a suitable viscosityagent is ethylene oxide polymer. According to the invention, this agentin concentration within the suspension of about 250 ppm, has been foundto provide the desired viscosity. Of course, other viscosity agentswould be well known to the person of ordinary skill in the art and arewell within the broad scope of the present invention. The suspension atthis point typically has a pH of between about 8 and about 10.

According to the invention, refractory inorganic carbide particles,preferably silicon carbide particles, are now mixed with the suspension.These particles preferably have an average particle size which is lessthan or equal to about 150 μm. This particle size has been found to helpprovide desirable surface area and pore volume properties in the endproduct. This mixture is mixed sufficiently to provide a substantiallyhomogenously mixed aqueous suspension of silica and silicon carbide.This material is now ready for forming into the desired shapes orportions in accordance with the present invention.

In order to form the aqueous suspension into the desired sphericalshape, the suspension is preferably formed into droplets by exposing thesuspension to an inert organic phase, preferably in the presence of anon-ionic surfactant. The difference in surface tension causes theaqueous suspension to form droplets, the size of which can be controlledthrough the application of different mixing intensity. This mixing iscarried out at least sufficiently to produce substantially uniformdroplet sizes within a suitable droplet size distribution, for example,between about 0.1 and about 3 mm, and preferably until at least about80% of the aqueous suspension is contained within a droplet sizedistribution between about 0.1 and about 0.4 mm in size. Of course,other methods known to a skilled artisan could be used to form thedroplets well within the broad scope of the present invention.

In accordance with one embodiment of the invention, this mixing step iscarried out sufficiently to produce an emulsion of the aqueoussuspension in the organic phase.

While many different inert organic phases could be used, especiallythose which are inert under the catalyst forming conditions and whenexposed to the aqueous suspension, preferred inert organic phasesinclude but are not limited to kerosene, hexane, toluene, mineral oil,vegetable oil, alcohol and combinations thereof.

Before mixing with the aqueous suspension, it may be desirable to heator otherwise provide the inert organic phase at a temperature of betweenabout 70 and about 120° C.

Either before mixing with the organic phase, or during this mixing,preferably before mixing, a gelling agent is added to the aqueoussuspension and serves to begin a partial solidification process of thecolloidal silica and silicon carbide within the suspension such thatwhen the desired droplets are formed, they are at least partiallysolidified.

Suitable gelling agents include but are not limited to ammonium salts,for example ammonium chlorides, nitrates, oxalates, sulfates, acetatesand the like. While these gelling agents are preferred, it should ofcourse be appreciated that other gelling agents would be known to aperson of skill in the art.

Ammonium salts are particularly preferred because they cause gelling byforming siloxane bonds while at the same time creating positive counterions to balance the negative surface charge of the silica source. Thesesiloxane bonds within the resulting droplets and eventual catalystsupport spheres are believed to be one factor in providing the desirableresults obtained with the catalyst support of the present invention.

The partially solidified droplets of silica-silicon carbide arerecovered from the organic phase, and then further processed to providethe catalyst support of the present invention. This involves drying andcalcining as will be further described below so as to provide thedesired catalyst support having desired properties.

According to the invention, the partially solidified droplets orspherical shaped portions are first aged and dried, preferably overnightor for a period of at least about 4 hours, at a temperature of betweenabout 70 and about 120° C., preferably about 90° C. The aged and driedcatalyst support spheres at this stage are now ready for calcining.

A first calcination is preferably carried out at a temperature ofbetween about 350 and about 700° C., preferably a temperature of about600° C., for a period of time sufficient to remove all traces of solventand additives from the original starting materials. This material isthen treated further in a hydrothermal treatment step.

The hydrothermal treatment step is preferably carried out at atemperature of between about 120° C. and about 250° C., and for a periodof time sufficient to collapse small pores in the support so as toprovide an average pore diameter of the support of at least about 150 Å,and preferably with no sign or indication of microporosity. This treatedmaterial is then preferably further calcined. The next calcinations isalso preferably carried out at a temperature of between about 350 andabout 700° C., preferably about 600° C., and produces a catalyst supportin the form of substantially spherical shapes of substantiallyhomogeneously distributed silica and silicon carbide, wherein thematerial has a surface area of at least about 65 m²/g, a particle sizeof at least about 0.1 mm, preferably between about 0.1 and about 3 mm, apore volume of at least about 0.2 cc/g, preferably between about 0.2 andabout 0.7 cc/g and more preferably at least about 0.4 cc/g, and anaverage pore diameter of at least about 150 Å.

The starting silica and silicon carbide materials are preferably addedto the aqueous suspension in amounts sufficient to provide the endingcatalyst support material containing between about 90% and about 50% wtof silica based upon weight of the catalyst support material, andcontaining between about 10 and about 50% wt of silicon carbide basedupon weight of the catalyst support material.

The catalyst support prepared according to the invention has excellentmaterial hardness or attrition resistance and heat dissipationproperties, even as compared to the material of the aforesaid U.S. Pat.No. 5,710,093. When subjected to an attrition test, material accordingto U.S. Pat. No. 5,710,093 showed a comparative attrition rate of 6.6,while material according to the invention showed less formation of finesand a comparative attrition rate of 6.0.

According to the invention, the final catalyst system is prepared bydepositing a catalytically active metal phase on the support. Accordingto the invention, a particularly suitable catalytically active metalphase has been found to include at least one metal selected from Group 4of the periodic table of elements, and at least one additional metalselected from the group consisting of Groups 8, 9 and 10 of the periodictable of elements.

Preferred Group 4 metals are zirconium (Zr), titanium (Ti) and hafnium(Hf), and mixtures thereof, and zirconium is particularly preferred.

Preferred metals from Groups 8, 9 and 10 include cobalt (Co), iron (Fe),nickel (Ni), Ruthenium (Ru) and mixtures thereof, and cobalt isparticularly preferred.

The catalyst system is preferably prepared so as to include Group 4metal in an amount between about 0.1 and about 25% wt based upon weightof the catalyst system (combined weight of the support and metal phase).The catalyst system is also preferably prepared so as to provide themetal from Groups 8, 9 and 10 in an amount of between about 1 and about50% wt based upon weight of the catalyst system.

The catalytically active metal phase can be provided on the supportusing any known technique, including but not limited to simultaneous orsequential impregnation, ion exchange and the like. Sequentialimpregnation with aqueous solution of the desired metal is particularlypreferred.

In order to impregnate with the metal, an aqueous solution is preferablyprepared by mixing a water soluble salt of the desired metal in water.Suitable examples of such salts include nitrates, oxalates, sulfates,acetates, acetylacetanates and mixtures thereof.

It is particularly preferred to impregnate the support first with theGroup 4 metal, and then to calcine the Group 4 impregnated support at atemperature of between about 350 and about 700° C. This material is thenimpregnated with the Group 8, 9 and 10 metal and the resulting twiceimpregnated material is then calcined again to produce the finalcatalyst system of the present invention which, as set forth above, hasexcellent application in connection with hydrogenation processes.

As set forth above, hydrogenation processes are utilized to converthydrocarbon feeds into more desirable products. According to theinvention, one particularly preferred process is the hydrogenation ofcarbon monoxide (CO) to produce CH₄, C₂ and C₂ ⁺. In such a process, acarbon monoxide feed is exposed to hydrogen and the catalyst system ofthe present invention, typically in a reactor such as an ebulliated bedreactor as discussed above, at hydrogenation temperature and pressure.These process conditions preferably include a temperature of betweenabout 200° C. and about 300° C., preferably about 220° C., and apressure of between about 250 psig and about 450 psig, preferably about360 psig, under a hydrogen to carbon monoxide ratio (H₂/CO) of betweenabout 1 and about 5, preferably about 2, and a gas-hydrogen spacevelocity (GHSV) of between about 1.5 and about 5.5 SLPH/kg-cat-h,preferably about 3.5 SLPH/kg-cat-h. According to the invention, thehydrogenation process using the catalyst system of the present inventionproduces a conversion rate to desired products of at least about 60%vol. based upon volume of the initial feed.

EXAMPLE 1

This example illustrates the preparation method of a catalyst supportaccording to the invention. A series of batches of catalyst supportconstituted homogenously of spherical particles of amorphous silica andsilicon carbide were prepared. Five suspensions of 305 g each wereprepared by mixing a colloidal silica (prepared in the laboratory usingsodium silicate) and mixing with silicon carbide having a particle sizeof less than or equal to 150 μm and ammonium salt as a gelling agent.

An ethylene oxide polymer (Poliox WSR-205, Union Carbide) was added tothe colloidal silica at a concentration of 250 ppm, to adjust theviscosity of the suspension or slurry to a value exceeding 10 cp at 25°C.

The suspension was then transferred to a vessel containing an inertorganic liquid and a non-ionic surfactant so that spherical droplets ofcatalyst support are formed. The ammonium salt begins the gellingprocess, thus, the spherically formed droplets of suspension are atleast partially solidified. The spheres were then recovered and driedovernight at 90° C. The dried spheres were then calcined at 600° C. soas to remove all traces of solvent. The spheres were then hydrothermallytreated at 180° C. and calcined again at 600° C. The resulting sphericalparticles had a pore volume of about 0.40 cc/g.

Five catalyst supports were prepared from the slurries in accordancewith the above procedure. The characteristics of each support are setforth in Table 1, below. TABLE 1 SURFACE AREA PORE VOLUME PORE DIAMETERSUPPORT m²/g cc/g Å 1 69 0.38 191 2 73 0.67 282 3 78 0.48 224 4 77 0.47209 5 78 0.43 197

EXAMPLE 2

This example illustrates the preparation of the catalyst support withdifferent particle size of silicon carbide in accordance with the aboveprocedure as described in Example 1. Two supports were prepared withsilicon carbide having particle size of less than 150 μm. The resultingspherical particles had an average particle size of about 0.25 mm. Thecharacteristics of each support are in Table 2, below. TABLE 2 SiCPARTICLE SURFACE PORE PORE SIZE AREA VOLUME DIAMETER SUPPORT (μm) (m²/g)(cc/g) Å 6 <100 78 0.40 188 7 <50 80 0.49 202

EXAMPLE 3

This example illustrates the preparation of a catalyst system in whichthe catalyst supports of Example 2 are impregnated with zirconium andcobalt. Two samples of catalyst support prepared in Example 2 were.co-impregnated with the desired active metals using a pore saturationmethod with solutions containing ZrO (NO₃). H₂O and Co(NO₃)₂.H₂O. Thecatalysts were prepared so as to contain 2% of zirconium per weight and15% of cobalt per weight. The impregnated supports were dried at 80° C.and calcined at 370° C. to oxidize the metal phase. The characteristicsof each impregnated support are in Table 3, below. TABLE 3 SURFACE POREPORE AREA VOLUME DIAMETER CATALYST SUPPORT (m²/g) (cc/g) Å A 6 63 0.31150 B 7 64 0.27 162

EXAMPLE 4

This example illustrates the silicon carbide particle size effect insidethe impregnated catalyst support. The conversion and productdistribution is obtained from hydrogenation of a carbon monoxidefeedstock at a temperature of 220° C., a pressure of 360 psig, ahydrocarbon to carbon monoxide ratio of 2, and GHSV of 3.5SLPH/kg-cat-h. The results of each reaction, carried out in a CSTRreactor, are shown in Table 4, below. TABLE 4 SiC PARTICLE PRODUCTS (%wt.) CONVERSION CATALYST (μm) CH₄ CO₂ C₂ ⁺ % A <100 5.6 0.9 93.5 62.3 B<50 6.0 1.0 93.0 61.3

As shown, the process using a catalyst according to the inventionproduced conversion rates greater than 60% vol., with excellentselectivity to C₂ ⁺ products.

It is to be understood that the invention is not limited to theillustrations described and shown herein, which are deemed to be merelyillustrative of the best modes of carrying out the invention, and whichare susceptible of modification of form, size, arrangement of parts anddetails of operation. The invention rather is intended to encompass allsuch modifications which are within its spirit and scope as defined bythe claims.

1-29. (canceled)
 30. A catalyst support, comprising substantiallyspherical particles having siloxane bonds of a substantially homogenousmixture of refractory inorganic oxide and refractory inorganic carbide,the support having a solid surface area of at least about 65 m²/g, aparticle size of at least about 0.1 mm, a pore volume of at least about0.2 cc/g, and an average pore diameter of at least about 150 Å.
 31. Thecatalyst support of claim 30, wherein the spherical catalyst support hasa particle size of between about 0.1 and about 3 mm.
 32. The catalystsupport of claim 30, wherein the spherical catalyst support has a porevolume of at least about 0.4 cc/g.
 33. The catalyst support of claim 30,wherein the spherical catalyst support has a pore volume of betweenabout 0.2 and about 0.7 cc/g.
 34. The catalyst support of claim 30,wherein the spherical catalyst support contains refractory inorganiccarbide in an amount between about 10 and about 50% wt based upon totalweight of the catalyst support.
 35. The catalyst support of claim 30,wherein the refractory inorganic oxide comprises silica, and therefractory inorganic carbide comprises silicon carbide.
 36. The catalystsupport of claim 30, further comprising a catalytically active metalphase on the catalyst support, wherein the catalytically active metalphase comprises at least one first metal selected from Group 4 of theperiodic table of elements, and at least one second metal selected fromthe group consisting of Groups 8, 9 and 10 of the periodic table ofelements.
 37. The catalyst support of claim 36, wherein the at least onefirst metal is selected from the group consisting of Zr, Ti, Hf, andmixtures thereof, and wherein the at least one second metal is selectedfrom the group consisting of Co, Fe, Ni, Ru and mixtures thereof. 38.The catalyst support of claim 36, wherein the at least one first metalis Zr and the at least one second metal is Co.
 39. The catalyst supportof claim 36, wherein the at least one first metal is present in anamount between about 0.1 and about 25% wt based upon combined weight ofthe catalyst support and the metal phase, and wherein the at least onesecond metal is present in an amount between about 1 and about 50% wtbased upon combined weight of the catalyst support and the metal phase.40-41. (canceled)